Anthracene dye and process of making same.



Yatented March 8, 1904.

UNITED STATEs PATENT OFFICE,

HEINRICH WELTZ, OF LUDWIGSHAFEN-ON-THE RHINE, GIERMANY, AS- SIGrNOR TO BADISCHE ANILIN UND SODA FABRIK, OF LUDWIGS- HAFEN-ON-THE-RHINE, GERMANY, A

MANY.

CORPORATION OF BADEN, GER- fiNTH RACENE DYE AND PROCESS OF MAKING SAME.

'srnorrroarron forming part of Letters Patent 1m 754,264, dated March 8, 1904.

Application filed A ix-i110, 1908. Serial No. 152,069. (No specimens.)

ful Improvements in A'nthracene Coloring-- Matters and Processes of Making Same, of which the following is a specification.

By the action on anthraquinon-beta-mono- :sulfo-acid of concentrated sulfuric acid and mercury or mercury salts in the presence of phosphoric acid or arsenic acid and nitrous acid a new poly-hydroxy-anthraquinon-sulfoacid can be. obtained which is regarded as a purpurin-sulfo-acid and will hereinafter be referred to as su ch. I have discovered that this purpurin sulfo-acid on being treated with aromatic amido compounds can be converted into valuable coloring-matters which can be directly employed for dyeing. The treatment can be efiected in an open or in a closed ves- ,3 sel with or without the addition of a solvent,

' such as water or alcohol, or of an agent assistmg the reaction, such as boric acid, salts of amide compounds, hydrochloric acid, hydroloromlc acid, hydrofluoric acid, sulfuric acid, phosphoric acid, benzoic acid, acetic acid,

zinc chlorid, salts of the aforementioned acids, l

and the like. As amido compounds there can be employed anilin, ortho-toluidin, para-toluidin, xylidin, para-phenylen-diamin, benzidin, alpha-naphthylamin, beta-naphthylamin,. and the like.

Suitable temperatures for carrymg out the reaction are in general those -between one hundred and twenty and one hundred and ninety degrees centigrade (120- 190 C. ;).but other temperatures may be em ployed. The products resulting from the re-.

action may or may not be homogenous.

The following examples will serve tofurther illustrate the nature of my invention, which, however, is not confined to these examples. The parts are by weight.

Example 1: Into one hundred and twenty (l20) parts of sulfuricacid (containing ninetysix (96) per cent. of H180) slowly introduce ten (10) parts of sodium nitrite while stirring well and then ten (10) .partsof dry anthrauinon-beta-mono-sulfo-acid sodium salt, one 5 1) part of meta-arsenic acid (containing about sixty-five per cent. AS2O5,) and one and one-fifth (1%) parts of mercury sulfate. Heat the whole gradually during two (2) hours to a temperature of twohundred and ten degrees 5 5 centigrade, (210 G.) The operation is to be stopped as soon as a test portionof the melt dissolved in Water yields on addition of causticsoda lye a blue-red coloration or until the solution in concentrated sulfuric acid is yellow- 60 red and on the addition of boric'acid becomes blue-red without the appearance of fluorescence. when cold, pour the whole into water, boil it upiadd sufficient common salt, and cool and filter off the product which separates out. 5

It can be purified by dissolving it in water and precipitating it by means of hydrochloric acid.

Example 2: Heat ten (10) parts of the prodnot such as can be obtained according'to. the 7 preceding Examplel with one hundred (100) parts of anilin in an autoclave at a temperature of one hundred and sixty degrees centigrade (160 C.) until; a test portion when treated with concentrated sulfuric acid does not yield a red, but a violet, solution. This is usually'the case in from three to four (34) hours. Remove the excess ofanilin from the reaction product by means of steam and salt but the new coloring-matter by means ofcommon salt,-or the melt can be poured into dilute hydrochloric acid, when the reaction product separates out. Collect by filtration, wash with dilute hydrochloric acid, anddry. It dyes unmordanted wool from the acid-bath violet 5 and dyes chrome-mordanted woo'l dark blue. Condensation can also be effected in an open vessel and with the addition of boric acid or a the like, ifdlesired.

Example 3: Dissolve ten (10) parts of the product such as can be obtained accordingto' the preceding Example 1 in forty (40) parts of water, Add fifty (50) parts of anihn and heat the whole in-a reflux apparatus at a temperature of one hundred and thirty-five degrees centigrade C.) until the mass becomes red-blue. Work up the product as'explained in the foregoing Example 2.

Example 4:: Heat together fifteen (15) parts of the product such as can be obtained according to the preceding Example 1, ten (10) partsof crystallized dry boric acid, and one hundred (100) parts of anilin at a tempera-r ture of one hundred and thirty-five degrees the case in two (2) hours, discontinue the heating and blow off the excess of anilinby means of steam. The coloring-matter so obtained (80) parts of absolute alcohol .at a temperature of one hundred and thirty-five degrees centigrade (135 C.) until a test portion dissolved in concentrated sulfuric acid yields a blue-red solution. When cold, pour the whole into dilute hydrochloric acid, collect the reaction product, and wash'it with dilute hydrochloric acid and dry it. It dyes wool mordanted with chrome bluish-black. On treatment on the fiber with chromates the shades become gray-blue.

The temperatures, the proportions, and the ingredients in the above examples may be varied within wide limits.

The following table presents some of the properties of some of the coloring-matters dyes unmordanted wool from the acid bath obtainable according to my invention;

7 Solution in con- A ueous solution A ueous solution Productot- Solution in anilin. geentrated sulg ifi fi (in addition o! (in addition of 1 (uric acid. no 'causiicsoda. ammonia.

Exampie2.... Reddish blue..... Violet Violet Green-blue Reg-blue topure Blue-violet.

V Example 4...- Blue-violet'. Red-violet Violet Reddish blue..." Blue Biue-violet.

Example 5.... Red-violet Red-violet Reddlshviolet.... Green-blue Violet Blue-red.

I'claim tion on the addition of boric acid'becomes 1. The process of manufacturing anthrablue, whose aqueous solution on the addition cene coloring-matter by treating anthraqui- .non-beta-mono-sulfo-acid with concentrated sulfuric, acid and mercury in the presence of phosphoric acid and nitrous acid and then treatingtheresultingpurpurin-sulfo-acid with an aromatic amido compound.

2. The. anthracene coloring-matter such as can be obtained by heating the hereinbeforedefined purpurin-sulfo-acid with an aromatic amido body, which dissolves in concentrated sulfuric acid with a violet color, which solu of caustic soda 'is blue to violet and on the addition of ammonia blue-violet to blue-red,

which dyes chrome-Inordanted wool black.

' In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

I v HEINRICH WELTZ.

Witnesses: i

"ER EST F. Emmaanr, 

